Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/882—Molybdenum and cobalt
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
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  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
  • B01J27/19—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J33/00—Protection of catalysts, e.g. by coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/617—500-1000 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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  • B01J35/618—Surface area more than 1000 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/651—50-500 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
  • B01J35/69—Pore distribution bimodal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0207—Pretreatment of the support
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1077—Vacuum residues
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • C—CHEMISTRY; METALLURGY
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  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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  • C10G2300/205—Metal content

Definitions

• the present invention relates to hydrotreating catalysts having a hydrodemetallation (HDM) favorable texture and formulation, while maintaining satisfactory hydrodesulfurization (HDS) activity, their preparation and their use.
• the invention consists of the use of mesoporous and macroporous catalysts supported on an aluminum oxide matrix comprising the group VI B and group VIII elements, as well as the phosphorus element. It has been discovered that this type of formulation associated with a support of specific textural properties makes it possible, particularly in the first catalytic beds of a process for the hydrotreatment of residues, in a fixed bed, but also in a bubbling bed process, to improve significantly the activity in hydrodemetallation (HDM) and stability over time.
• HDM hydrodemetallation
• the fixed bed residue hydrotreating processes (commonly called "Residual Desulfurization” unit or RDS) lead to high refining performance: typically they can produce a boiling temperature cut above 370 ° C. containing less than 0 ° C. , 5% by weight of sulfur and less than 20 ppm of metals from fillers containing up to 5% by weight of sulfur and up to 250 ppm of metals (Ni + V).
• the various effluents thus obtained can serve as a basis for the production of heavy-duty heavy-duty fuels and / or pre-treated feeds for other units such as catalytic cracking ("Fluid Catalytic Cracking").
• the hydroconversion of the residue into slices lighter than the atmospheric residue is generally low, typically of the order of 10 to 20% by weight.
• the feed previously mixed with hydrogen, circulates through several fixed bed reactors arranged in series and filled with catalysts.
• the total pressure is typically between 100 and 200 bar (10-20 MPa) and the temperatures between 340 and 420 ° C.
• the effluents withdrawn from the last reactor are sent to a fractionation section.
• the fixed bed hydrotreating process consists of at least two steps (or sections).
• the first so-called hydrodemetallation (HDM) stage is mainly aimed at eliminating the majority of metals from the feedstock by using one or more hydrodemetallization catalysts.
• This stage mainly includes vanadium and nickel removal operations and, to a lesser extent, iron.
• the second or so-called hydrodesulphurization (HDS) stage consists in passing the product of the first stage over one or more hydrodesulfurization catalysts, which are more active in terms of hydrodesulfurization and hydrogenation of the feedstock, but less tolerant to metals.
• the catalyst For the hydrodemetallation (HDM) stage, the catalyst must be able to treat metal and asphaltene-rich fillers, while having a high demetallizing power associated with a high metal retention capacity and high coking resistance.
• Catalysts having a bimodal porous distribution making it possible to achieve high hydrodemetallation yields have been described in US Pat. No. 5,221,666. The advantage of such a porous distribution is also highlighted in US Pat. Nos. 5,089,463 and US Pat.
• the initial active phase of the catalyst placed in the hydrodemetallization step is generally composed of nickel and molybdenum, and possibly of dopants such as phosphorus. This active phase is known to be more hydrogenating than a phase consisting of cobalt and molybdenum, also used sometimes, and thus limits the formation of coke in the porosity and thus the deactivation.
• the catalyst For the hydrodesulfurization step (HDS), the catalyst must have a high hydrogenolysing potential so as to carry out a deep refining of the products: desulfurization, further demetallation, lowering of the Carbon Conradson content (Carbon Conradson Residue: CCR) and asphaltenes content.
• a catalyst is characterized by a low macroporous volume (US 6,589,908).
• US Pat. No. 4,818,743 teaches that the porous distribution can be monopopulated between 1 and 13 nm or bipopulated. with a relative difference between the two populations which can vary from 1 to 20 nm, as in US Pat. No. 6,589,908.
• the active phase of the catalyst placed in the hydrodesulphurization stage is generally composed of cobalt and molybdenum, like this is described in US Patent 6,332,976.
• 6,780,817 teaches that it is necessary to use a catalyst support that has at least 0.32 ml / g macroporous volume for stable fixed bed operation.
• a catalyst further has a median diameter in the mesopores of 8 to 13 nm and a high specific surface area of at least 180 m 2 / g.
• US Pat. No. 6,919,294 also describes the use of so-called bimodal, therefore mesoporous and macroporous carriers, with the use of high macroporous volumes, but with a mesoporous volume limited to not more than 0.4 ml / g. US Pat. Nos.
• 4,976,848 and 5,089,463 disclose a heavy charge hydrodemetallation and hydrodesulphurisation catalyst comprising a hydrogenating active phase based on Group VI and VIII metals and an inorganic refractory oxide support, the catalyst having precisely between 5 and 1 1% of its pore volume in the form of macropores and has mesopores with a median diameter greater than 16.5 nm.
• US Pat. No. 7,169,294 describes a heavy-weight hydroconversion catalyst comprising between 7 and 20% of Group VI metal and between 0.5 and 6% by weight of Group VIII metal on an aluminum support.
• the catalyst has a specific surface area of between 100 and 180 m 2 / g, a total pore volume greater than or equal to 0.55 ml / g, and at least 50% of the total pore volume is included in pores larger than 20 nm.
• At least 5% of the total pore volume is comprised in pores larger than 100 nm, at least 85% of the total pore volume being included in pores between 10 and 120 nm in size, less than 2% of pore volume total being contained in pores with a diameter greater than 400 nm, and less than 1% of the total pore volume being contained in pores with a diameter greater than 1000 nm.
• Numerous developments include the optimization of the porous distribution of the catalyst or catalyst mixtures by optimizing the catalyst support.
• US Pat. No. 6,589,908 describes, for example, a process for preparing an alumina characterized by the absence of macropores, less than 5% of the total pore volume constituted by pores with a diameter of greater than 35 nm, and a high pore volume greater than 0.8 ml / g, and a bimodal mesopore distribution in which the two modes are separated by 1 to 20 nm and the primary porous mode being larger than the porous median diameter.
• the method of preparation described implements two stages of precipitation of alumina precursors under well-controlled conditions of temperature, pH and flow rates. The first step operates at a temperature between 25 and 60 ° C, a pH between 3 and 10.
• the suspension is then heated to a temperature between 50 and 90 ° C.
• Reagents are again added to the slurry, which is then washed, dried, shaped and calcined to form a catalyst support.
• Said support is then impregnated with an active phase solution to obtain a hydrotreatment catalyst; a catalyst for hydrotreating residues on a mesoporous monomodal support of porous median diameter around 20 nm is described.
• the patent application WO 2004/052534 A1 describes the use in hydrotreatment of heavy hydrocarbon feeds of a mixture of two catalysts with supports having different porous characteristics, the first catalyst having more than half the pore volume in the pores of diameter greater than 20 nm, 10 to 30% of the pore volume being contained in the pores of diameter greater than 200 nm, the total pore volume being greater than 0.55 ml / g, the second having more than 75% of the pore volume content in pores with a diameter of between 10 and 120 nm, less than 2% in pores with a diameter greater than 400 nm and 0 to 1% in pores with a diameter greater than 1000 nm.
• the method of preparation described for the preparation of these catalysts implements a step of coprecipitation of aluminum sulphate with sodium aluminate, the gel obtained is then dried, extruded and calcined. It is possible to add silica during or after coprecipitation. Adjusting the layout provides the characteristics of the media.
• Group VIB, VII, IA or V metals may be incorporated in the support, by impregnation and / or by incorporation into the support before it is shaped into particles. Impregnation is preferred.
• US Pat. No. 7,790,652 describes hydroconversion catalysts that can be obtained by coprecipitation of an alumina gel, then introduction of metals onto the support obtained by any method known to those skilled in the art, in particular by impregnation. The resulting catalyst has a monomodal distribution with a mesoporous median diameter of between 11 and 12.6 nm and a porous distribution width of less than 3.3 nm.
• the patent application WO2012 / 021386 discloses hydrotreatment catalysts comprising a porous refractory oxide support shaped to from alumina powder and from 5% to 45% by weight of catalyst fines.
• the support comprising the fines is then dried and calcined.
• the support obtained has a specific surface area of between 50 m 2 / g and 450 m 2 / g, a mean pore diameter of between 50 and 200 ⁇ , and a total pore volume exceeding 0.55 cm 3 / g.
• the support thus comprises metal incorporated thanks to the metals contained in the catalyst fines.
• the resulting support can be treated with a chelating agent.
• the pore volume may be partially filled by means of a polar additive, and may be impregnated with a metal impregnating solution.
• a hydroconversion catalyst having both a bimodal porosity, with a high mesoporous volume coupled to a macroporous volume, a very high mesopore median diameter, and a impregnated hydro-dehydrogenating active phase.
• the increase in porosity is often at the expense of the specific surface area, and the mechanical strength.
• a catalyst prepared from an alumina resulting from the calcination of a specific alumina gel having a targeted alumina content, by impregnation of a hydro-dehydrogenating active phase on a support comprising mainly calcined alumina had a particularly interesting porous structure with an active phase content suitable for the hydrotreatment of heavy loads, especially for hydrodemetallation reactions.
• the present invention relates to the preparation of a catalyst comprising at least one group VI B element, optionally at least one group VIII element and optionally the phosphorus element supported on an aluminum oxide support having particular textural properties.
• said support having in particular a high total pore volume (greater than or equal to 0.80 ml / g), a high mesopore median diameter (greater than or equal to 18 nm), a mesoporous volume of at least 0.70 ml / g, a macroporous volume of between 10 and 35% of the total pore volume, a macroporous median diameter of between 100 and 1200 nm, its BET specific surface area moreover remaining greater than 1 10 m 2 / g, said method comprising at least the following steps:
• the invention also relates to the catalyst that can be prepared by the process of preparation described.
• the invention finally relates to the use of this catalyst in hydrotreating or hydroconversion processes of heavy hydrocarbon feedstocks, in particular highly concentrated metal feedstocks (for example nickel and vanadium, with concentrations exceeding 50 ppm).
• highly concentrated metal feedstocks for example nickel and vanadium, with concentrations exceeding 50 ppm.
• the invention relates to a method for preparing a hydroconversion catalyst comprising:
• hydro-dehydrogenating active phase comprising at least one Group VIB metal of the periodic table of elements, optionally at least one metal of group VIII of the periodic table of the elements, optionally phosphorus,
• said catalyst having:
• a mesoporous volume as measured by mercury porosimeter intrusion greater than or equal to 0.65 ml / g
• a macroporous volume of between 15 and 40% of the total pore volume
• said method comprising at least the following steps:
• step a) a step of dissolving an aluminum acid precursor chosen from aluminum sulphate, aluminum chloride and aluminum nitrate in water, at a temperature of between 20 and 90 ° C. at a pH of between 0.5 and 5 for a period of between 2 and 60 minutes; b) A step of adjusting the pH by adding to the suspension obtained in step a) at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, hydroxide and the like.
• step b) a step of coprecipitation of the suspension obtained at the end of step b) by adding to the suspension at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, at least one of the basic or acidic precursors comprising aluminum, the relative flow rate of the acidic and basic precursors being chosen so as to obtain a pH of the reaction medium of between 7 and 10 and the flow rate of the acid precursor (s) and aluminum-containing basic being adjusted so as to obtain a final alumina concentration in the suspension of between 10 and 38 g / L; d) a filtration step of the suspension obtained at the end of the co-precipitation step
• step e) a step of drying said alumina gel obtained in step d) to obtain a powder
• step f) a step of shaping the powder obtained at the end of step e) to obtain a raw material
• g) a step of heat treatment of the raw material obtained at the end of step f) at a temperature of between 500 and 1000 ° C., with or without a flow of air containing up to 60% by volume of water, to obtain an aluminum oxide support;
• the alumina concentration of the alumina gel suspension obtained in step c) is preferably between 13 and 35 g / l, very preferably between 15 and 33 g / l.
• the acidic precursor is aluminum sulphate.
• the basic precursor is sodium aluminate.
• the aqueous reaction medium is water and said steps operate with stirring, in the absence of organic additive.
• the acidic precursor of step a) is introduced in an amount corresponding to 0.5 to 4% by weight of the total alumina formed at the end of step c).
• the invention also relates to a mesoporous and macroporous hydroconversion catalyst that can be prepared by the above method.
• the catalyst has:
• a mesoporous volume as measured by mercury porosimeter intrusion greater than or equal to 0.70 ml / g
• a macroporous volume of between 17 and 35% of the total pore volume
• the catalyst has a macroporous volume of between 20 and 30% of the total pore volume.
• the catalyst has a mesoporous median diameter in volume determined by mercury porosimeter intrusion of between 19 and 25 nm and a macroporous median volume diameter of between 10 and 1000 nm, inclusive.
• the group VI B metal content is advantageously between 2 and 10% by weight of Group VI B metal trioxide relative to the total mass of the catalyst.
• the group VIII metal content is advantageously between 0.00 and 3.6% by weight of the Group VIII metal oxide with respect to the total mass of the catalyst,
• the phosphorus element content is advantageously between 0.degree. at 5% by weight of phosphorus pentoxide relative to the total mass of the catalyst.
• the hydro-dehydrogenating active phase is composed of molybdenum or nickel and molybdenum or cobalt and molybdenum.
• the hydro-dehydrogenating active phase also comprises phosphorus.
• the invention also relates to a process for the hydrotreatment of a heavy hydrocarbon feedstock chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, hydroconversion fixed bed, bubbling bed or moving bed, taken alone or in mixture, comprising contacting said feed with a hydroconversion catalyst according to the invention or prepared according to the preparation process according to the invention.
• Said hydrotreatment process may be carried out partly in a bubbling bed at a temperature of between 320 and 450 ° C., under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity advantageously between 0.1 and 10 volumes of filler per volume of catalyst and per hour, and with a hydrogen gas ratio on hydrocarbon liquid feed advantageously between 100 and 3000 normal cubic meters per cubic meter.
• the said hydrotreatment process may be carried out at least in part in a fixed bed at a temperature of between 320 ° C. and 450 ° C., at a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity of between 0.degree. 5 and 5 volume of filler per volume of catalyst per hour, and with a hydrogen gas ratio on hydrocarbon liquid feed of between 200 and 5000 normal cubic meters per cubic meter.
• the process may be a process for the hydrotreatment of a heavy hydrocarbon feedstock of the fixed bed residue type comprising at least:
• hydroconversion catalyst is used in at least one of said steps a) and b).
• said hydroconversion catalyst is used in the first catalytic beds of the hydrodemetallation step a).
• the process may be a hydrotreatment process for a heavy hydrocarbon feedstock in a bubbling bed, wherein the feedstock has a cumulative metal content of 50 ppm or more and said hydroconversion catalyst is used for the hydrodemetallization reactions.
• FIG. 1 shows the evolution at 300 hours of the relative hydrodemetallation performances of the catalysts A1, AA1, and E1 on a charge No. 1 comprising a mixture of atmospheric residue and residue under vacuum (RAAM / RSVAL).
• FIG. 2 shows the evolution at 300 hours of the relative HDS hydrodesulphurization performance of the catalysts A1, AA1, and E1 on a No. 1 feedstock comprising a mixture of atmospheric residue and vacuum residue (RAAM / RSVAL).
• Figure 3 shows the evolution at 300 hours of relative HDM hydrodemetallation performance of catalysts A1, CA1, B1, D1 and E1 on a load No. 2 comprising a mixture of atmospheric residue and vacuum residue (RAAM / RSVAL).
• FIG. 4 shows the evolution at 300 hours of the relative HDS hydrodesulphurization performance of the catalysts A1, CA1, B1, D1 and E1 on a charge No. 2 comprising a mixture of atmospheric residue and vacuum residue (RAAM / RSVAL).
• FIG. 5 shows the evolution at 300 hours of the relative hydrodemetallation performances of the catalysts A1 and E1 on a charge No. 2 comprising a mixture of atmospheric residue and vacuum residue (RAAM / RSVAL).
• FIG. 6 shows the evolution at 300 hours of the relative HDS hydrodesulfurization performances of the catalysts A1 and E1 on a charge No. 2 comprising a mixture of atmospheric residue and vacuum residue (RAAM / RSVAL).
• the catalyst and support of the present invention have a specific porous distribution, where the macroporous and mesoporous volumes are measured by mercury intrusion and the microporous volume is measured by nitrogen adsorption.
• Macropores means pores whose opening is greater than 50 nm.
• pores is meant pores whose opening is between 2 nm and 50 nm, limits included.
• micropores pores whose opening is less than 2 nm.
• specific surface area refers to the BET specific surface area determined by nitrogen adsorption in accordance with ASTM D 3663-78, based on the BRUNAUER-EMMETT-TELLER method described in US Pat. Periodical "The Journal of the American Society", 60, 309, (1938).
• the total pore volume of the alumina or of the support or of the catalyst is understood to mean the volume measured by mercury porosimeter intrusion according to the ASTM D4284-83 standard at a maximum pressure of 4000. bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °. The angle of wetting was taken equal to 140 ° following the recommendations of the book "Techniques of the engineer, treated analysis and characterization", P 1050-5, written by Jean Charpin and Bernard Rasneur.
• the value of the total pore volume in ml / g given in the following text corresponds to the value of the total mercury volume (total pore volume measured by mercury porosimeter intrusion) in ml / g measured on the sample minus the mercury volume value in ml / g measured on the same sample for a pressure corresponding to 30 psi (approximately 0.2 MPa).
• the volume of macropores and mesopores is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °.
• the value at which mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond this mercury enters the pores of the sample.
• the macroporous volume of the catalyst or support is defined as the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm.
• the mesoporous volume of the catalyst or support is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm.
• the micropore volume is measured by nitrogen porosimetry.
• the quantitative analysis of the microporosity is carried out using the "t" method (Lippens-De Boer method, 1965) which corresponds to a transformation of the starting adsorption isotherm as described in the book “Adsorption by powders and porous solids. Principles, methodology and applications "written by F. Rouquérol, J. Rouquérol and K. Sing, Academy Press, 1999.
• the mesoporous median diameter is also defined as a diameter such that all pores less than this diameter constitute 50% of the total mesoporous volume determined by mercury porosimeter intrusion.
• Macroporous median diameter is also defined as a diameter such that all pores smaller than this diameter constitute 50% of the total macroporous volume determined by mercury porosimeter intrusion.
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• the combination of at least one group VI B element, optionally at least one group VIII element and optionally the phosphorus element with an aluminum oxide which simultaneously has a high pore volume (> 0.80 ml / g), a high mesopore median diameter (greater than or equal to 18 nm), and thus a BET surface area greater than 1 10 m 2 / g, leads to a catalyst with particular textural properties which has a significant gain of hydrodemetallation in a fixed bed process or in a bubbling bed process treating heavy hydrocarbon feeds, especially feeds containing more than 50 ppm of cumulated metals.
• the mesoporous amorphous support comes from the shaping of an alumina gel having a controlled alumina content, said alumina gel being obtained by precipitation of at least one aluminum salt.
• This catalyst in the first catalytic beds of a fixed bed process or in a bubbling bed process treating highly concentrated metal charges, allows a significant gain of hydrodemetallation, and therefore requires a lower operating temperature the catalysts of the prior art to achieve the same level of conversion of the metallated compounds. A gain in stability over time is also observed.
• the catalyst that may be prepared according to the invention is in the form of a calcined, predominantly aluminum oxide support on which the metals of the active phase are distributed.
• the support is subject to specific characteristics which are described below, as well as, to a lesser extent, the active phase and its formulation. Also described below, according to the invention, their preparations as well as the use of the catalyst in processes for hydrotreatment of heavy hydrocarbon feeds.
• the Group VI B metals are advantageously selected from molybdenum and tungsten, and preferably said Group VI B metal is molybdenum.
• Group VIII metals are preferably selected from iron, nickel or cobalt and nickel or cobalt, or a combination of both, is preferred.
• the respective amounts of group VI B metal and group VIII metal are advantageously such that the atomic ratio metal (aux) of Group VIII on metal (A) of group VI B (VllhVI B) is between 0.0: 1 And 0.7: 1 .0, preferably 0.05: 1 .0 and 0.7: 1 .0, very preferably between 0.1: 1 .0 and 0.6: 1 .0 and even more preferably between 0.2: 1 .0 and 0.5: 1 .0.
• This ratio can in particular be adjusted according to the type of load and the process used.
• the respective amounts of group VI B metal and phosphorus are such that the atomic phosphorus to metal group (A) ratio of group VI B (P / VI B) is between 0.0: 1.0 and 1.0: 1. , 0, preferably between 0.4: 1.0 and 0.9: 1.0, and even more preferably between 0.5, 1.0 and 0.85: 1.0.
• the metal content of group VI B is advantageously between 2 and 10% by weight of trioxide of at least Group VI B metal relative to the total mass of the catalyst, preferably between 3 and 8% and even more preferred between 4 and 7% by weight.
• the metal content of group VIII is advantageously between 0.0 and 3.6%, especially between 0.25 and 3.6% by weight, preferably between 0.4 and 2.5% by weight of the at least one group VIII metal oxide with respect to the total mass of the catalyst, very preferably between 0.6 and 3.7% by weight, and still more preferably between 1, 2 and 2.8% weight.
• the content of phosphorus element is advantageously between 0 and 5% by weight, preferably between 0.2 and 5.0% by weight of phosphorus pentoxide relative to the total mass of the catalyst, very preferably between 0.6 and 3.5% by weight and even more preferably between 1.0 and 3.0% by weight.
• Said catalyst based on the porous aluminum oxide according to the invention is generally presented in all the forms known to those skilled in the art.
• it consists of extrudates of diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm.
• This may advantageously be in the form of extruded cylindrical, trilobed or quadrilobed.
• its form is multilobed, trilobal or quadrilobed.
• the shape of the lobes can be adjusted according to all known methods of the prior art.
• the support of the catalyst according to the invention mainly comprises a porous aluminum oxide.
• the support consists exclusively of alumina.
• the support of said catalyst according to the invention generally comprises an alumina content greater than or equal to 90% and a silica content in SiO 2 equivalent of at most 10% by weight relative to the final oxide, preferably a silica content. less than 5% by weight, very preferably less than 2% by weight.
• the silica may be introduced by any technique known to those skilled in the art, for example during the synthesis of the alumina gel or during the comalaxing step.
• the support used for the preparation of the catalyst according to the invention advantageously has a total pore volume (VPT) of at least 0.80 ml / g, preferably at least 0.90 ml / g, and very preferably at least 0.95 ml / g.
• VPT total pore volume
• the support used according to the invention advantageously has a macroporous volume, V 50 nm, defined as the pore volume of diameter greater than 50 nm, between 10 and 35% of the total pore volume, preferably between 15 and 30% of the volume. total porous, and very preferably between 20 and 30% of the total pore volume.
• the support used according to the invention advantageously has a mesoporous volume, V meso , defined as the volume of the pores with a diameter of between 2 and 50 nm, inclusive limits, of at least 0.70 ml / g, and preferably of at least 0.75 ml / g.
• the mesoporous median diameter (D p meso ), the mesoporous volume being the volume corresponding to pores with a diameter of between 2 and 50 nm, limits included, is advantageously between 18 and 25 nm, preferably between 19 and 23 nm, very preferably between 20 nm and 23 nm, limits included.
• the macroporous median diameter (D p ma C ro), the macroporous volume, V 50 nm, being defined as the pore volume with a diameter greater than 50 nm, is advantageously between 100 nm and 1200 nm, preferably between 10 nm. and 1000 nm, very preferably between 120 and 800 nm.
• the catalyst support according to the present invention advantageously has a BET (S B ET) specific surface area of at least 1 10 m 2 / g, preferably at least 120 m 2 / g and even more preferably between 120 and 160 m 2 / g.
• BET surface is meant the specific surface area determined by nitrogen adsorption according to ASTM D 3663-78 established from the method BRUNAUER - EMMET - TELLER described in the journal "The Journal of the American Chemical Society", 60 , 309 (1938).
• the method of preparation according to the present invention has the particular advantage of leading to a porous aluminum oxide support having a mechanical strength quite satisfactory with respect to the porous volumes which characterize it, said resistance being materialized by the value of the crushing grain at EGG grain, preferably at least 0.5 daN / mm, very preferably at least 0.8 daN / mm.
• the method of measuring grain to grain crushing consists of measuring the maximum compressive force that an extruded material can withstand before it breaks, when the product is placed between two planes moving at a constant speed of 5 cm / min. . The compression is applied perpendicularly to one of the generators of the extrusion, and the grain to grain crushing is expressed as the ratio of the force to the length of the generator of the extruded.
• the finished catalyst that is to say with the metals deposited on its surface by any method known to those skilled in the art, as described below, therefore has the textural properties to follow.
• the catalyst according to the invention advantageously has a total pore volume (VPT) of at least 0.75 ml / g, preferably at least 0.85 ml / g, and very preferably at least 0, 90 ml / g, as determined by mercury porosimeter intrusion.
• VPT total pore volume
• the catalyst used according to the invention advantageously has a macroporous volume, V 50 nm between 15 and 40% of the total pore volume, preferably between 17 and 35% of the total pore volume.
• the macroporous volume represents between 20 and 30% of the total pore volume.
• the mesoporous volume, V meso , of the catalyst is at least 0.65 ml / g, and preferably at least 0.70 ml / g.
• the median mesoporous diameter is advantageously between 18 nm and 26 nm, preferably between 19 nm and 25 nm and very preferably between 20 and 24 nm, limits included.
• the median macroporous diameter is advantageously between 100 and 1200 nm, preferably between 1 and 1000 nm, very preferably between 120 and 800 nm, inclusive.
• the catalyst used according to the present invention advantageously has a BET (S B ET) specific surface area of at least 100 m 2 / g, preferably at least 1 m 2 / g and even more preferably between 120 and 150 m 2 / g.
• the porous aluminum oxide used in the support of the catalyst according to the present invention is a macroporous and mesoporous bimodal aluminum porous oxide.
• the mesoporous aluminum porous oxide is free of micropores.
• the porous aluminum oxide advantageously has a specific surface area greater than 1 m 2 / g.
• the specific surface area of the porous aluminum oxide is greater than 120 m 2 / g.
• the specific surface area of the porous aluminum oxide is between 120 and 160 m 2 / g.
• the mesoporous volume defined as the pore volume having a median diameter between 2 and 50 nm, is measured by mercury porosimetry.
• the mesoporous volume of the porous aluminum oxide is greater than or equal to 0.70 ml / g, very preferably greater than or equal to 0.75 ml / g.
• the porous aluminum oxide support of said catalyst according to the invention generally comprises an alumina content of greater than or equal to 90% and a silica content equivalent to SiO 2 of at most 10% by weight relative to the final oxide, preferably silica content of less than 5% by weight, very preferably less than 2% weight.
• the silica may be introduced by any technique known to those skilled in the art, for example during the synthesis of the alumina gel or during the comalaxing step.
• the aluminum oxide support according to the invention consists exclusively of alumina.
• the aluminum oxide support according to the invention is a non-mesostructured alumina.
• the porous aluminum oxide support prepared according to the invention is obtained by filtration, drying, shaping and heat treatment of a specific alumina gel.
• the preparation of said alumina gel comprises three successive stages: a) step of dissolving an acid precursor of alumina, b) step of adjusting the pH of the suspension using a basic precursor, and c) step of coprecipitating at least one acidic precursor and at least one basic precursor, at least one of which contains aluminum.
• the final alumina concentration in the suspension must be between 10 and 38 g / l, preferably between 13 and 35 g / l and more preferably between 15 and 33 g / l.
• Step a) is a step of dissolving an aluminum acid precursor in water, carried out at a temperature of between 20 and 80 ° C, preferably between 20 and 75 ° C and more preferred between 30 and 70 ° C.
• the aluminum acid precursor is chosen from aluminum sulphate, aluminum chloride and aluminum nitrate, preferably aluminum sulphate.
• the pH of the suspension obtained is between 0.5 and 5, preferably between 1 and 4, preferably between 1.5 and 3.5.
• This step advantageously contributes to a quantity of alumina introduced relative to the final alumina of between 0.5 and 4% by weight, preferably between 1 and 3% by weight, very preferably between 1.5 and 2.5%. weight.
• the suspension is left stirring for a period of between 2 and 60 minutes, and preferably 5 to 30 minutes.
• the step of adjusting the pH b) consists in adding to the suspension obtained in step a) at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide.
• the basic precursor is an alumina precursor chosen from sodium aluminate and potassium aluminate.
• the basic precursor is sodium aluminate.
• Step b) is carried out at a temperature between 20 and 90 ° C, preferably between 20 and 80 ° C and more preferably between 30 and 70 ° C and at a pH between 7 and 10, preferably between 8 and 10, preferably between 8.5 and 10 and very preferably between 8.7 and 9.9.
• the duration of step b) of pH adjustment is between 5 and 30 minutes, preferably between 8 and 25 minutes, and very preferably between 10 and 20 minutes.
• Step of coprecipitation Step c) is a precipitation step by bringing into contact, in an aqueous reaction medium, at least one basic precursor chosen from sodium aluminate, potassium aluminate, and ammonia.
• the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 7 and 10 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a final alumina concentration. in the suspension of between 10 and 38 g / l, preferably between 13 and 35 g / l and more preferably between 15 and 33 g / l.
• the co-precipitation step is conducted at a temperature between 20 and 90 ° C, and more preferably between 30 and 70 ° C.
• the precipitation step c) is carried out at a pH of between 7 and 10, preferably between 8 and 10, preferably between 8.5 and 10 and very preferably between 8.7 and 9.9.
• Step c) of coprecipitation is carried out for a period of between 1 and 60 minutes, and preferably of 5 to 45 minutes.
• steps a), b) and c) are carried out in the absence of organic additive.
• the synthesis of the alumina gel (steps a), b) and c)) is carried out with stirring.
• the process for preparing the alumina according to the invention also comprises a step of filtering the suspension obtained at the end of step c).
• Said filtration step is carried out according to the methods known to those skilled in the art.
• Said filtration step is advantageously followed by at least one washing step, with an aqueous solution, preferably with water and preferably from one to three washing steps, with a quantity of water equal to the amount of water. precipitate filtered.
• e) Drying step According to the invention, the alumina gel obtained at the end of the precipitation step c), followed by a filtration step d), is dried in a drying step e) for obtaining a powder, said drying step being advantageously carried out by drying at a temperature greater than or equal to 120 ° C. or by atomization or by any other drying technique known to those skilled in the art.
• said drying step e) may advantageously be carried out in a closed and ventilated oven.
• said drying step operates at a temperature between 120 and 300 ° C, very preferably at a temperature between 150 and 250 ° C.
• said drying step e) is carried out by atomization, the cake obtained at the end of the co-precipitation step, followed by a filtration step, is resuspended. Said suspension is then sprayed in fine droplets, in a vertical cylindrical chamber in contact with a stream of hot air to evaporate the water according to the principle well known to those skilled in the art.
• the powder obtained is driven by the heat flow to a cyclone or a bag filter that will separate the air from the powder.
• drying step e) is carried out by atomization
• the atomization is carried out according to the operating protocol described in the publication Asep Bayu Dani Nandiyanto, Kikuo Okuyama, Advanced Powder Technology, 22, 1-19 , 201 1. f) Formatting stage
• the powder obtained at the end of the drying step e) is formed in a step f) to obtain a green material.
• raw material is meant the material shaped and having not undergone any heat treatment steps.
• said shaping step f) is carried out by extrusion kneading, by granulation, by the technique of oil drop (drip or coagulation of drop in French), by pelletization.
• said shaping step f) is carried out by kneading - extrusion.
• the shaping is advantageously carried out with an acid level (total, expressed relative to dry alumina) of between 0 and 4% and preferably between 0.5 and 1.5%, a degree of neutralization of between 0.degree. and 200% and preferably between 0 and 40%.
• the acid and basic fire losses are advantageously between 60 and 70%.
• the raw material obtained at the end of the shaping step f) then undergoes a step g) of heat treatment at a temperature of between 500 and 1000 ° C., for a period advantageously between 2 and 10 hours, with or without a flow of air containing up to 60% water volume.
• said heat treatment is carried out in the presence of an air flow containing water.
• said heat treatment step g) operates at a temperature of between 540 ° C and 850 ° C.
• said g) heat treatment step operates for a period of between 2h and 10h.
• Said step g) heat treatment allows the transition of the boehmite to the final alumina.
• the heat treatment step may be preceded by drying at a temperature between 50 ° C and 120 ° C, according to any technique known to those skilled in the art.
• the preparation process according to the invention makes it possible to obtain a macroporous and mesoporous bimodal amorphous alumina porous oxide with a high mesoporous median diameter, greater than or equal to 18 nm, determined on the porous volume distribution curve by porosimeter intrusion. mercury.
• the mesoporous aluminum oxide support prepared according to the process of the invention is advantageously free of micropores. The absence of micropores is verified by nitrogen porosimetry.
• the mesoporous alumina support according to the invention advantageously has a mesoporous volume, that is to say contained in pores with a diameter of between 2 and 50 nm, as measured by mercury porosimeter intrusion, greater than or equal to 0.70 ml / g, preferably greater than or equal to 0.75 ml / g.
• the total pore volume measured by mercury porosimetry is advantageously greater than 0.80 ml / g.
• the mesoporous alumina oxide support according to the invention generally comprises a macroporous volume, V 50 nm, defined as the volume of pores with a diameter greater than 50 nm, as measured by mercury porosimeter intrusion, of between 10 and 35% of the volume. total porous and preferably between 15 and 30% of the total pore volume. In a very preferred embodiment, the macroporous volume represents between 20 and 30% of the total pore volume.
• the mesoporous alumina support according to the invention generally has a specific surface area greater than 1 m 2 / g.
• the support of the catalyst according to the invention comprises for the most part (at least 90% by weight) an aluminum oxide as described above and may also contain dopants such as silicon, titanium and zirconium elements (up to a content of 10% weight).
• the support of the catalyst according to the invention described above is usually used in the form of powder, beads, pellets, granules or extrudates, the shaping operations being carried out according to the conventional techniques known to man. of career. Examples include extrusion, pelletizing, oil drop, or turntable granulation methods.
• the catalyst according to the invention is obtained by depositing at least one Group VIB metal, optionally at least one Group VIII metal and optionally other elements such as the phosphorus element on the support of the catalyst according to the invention. described above.
• Said deposition can be carried out according to all the methods known to those skilled in the art.
• said deposition on alumina previously described can be achieved by all the impregnation methods known to those skilled in the art, including dry impregnation.
• at least one Group VIB metal, optionally at least one Group VIII metal and optionally the phosphorus element are deposited by dry impregnation of their associated compounds on the oxide support according to the invention.
• the deposition can be carried out via a single step of dry impregnation of the oxide support according to the invention via the use of a solution simultaneously containing at least one compound of at least one Group VIB metal, optionally at least one compound phosphorus, and optionally at least one compound of at least one Group VIII metal.
• the deposit can also be advantageously achieved via at least two cycles of dry impregnation.
• the different elements can thus be advantageously impregnated successively or one of the elements can also be impregnated into several sequences.
• One of the impregnations that is carried out can in particular be used for the use of an organic compound that the skilled person wishes to introduce in addition to the constituent elements of the final catalyst.
• the said solution (s) may be aqueous, consisting of an organic solvent or a mixture of water and at least one organic solvent (for example ethanol or toluene).
• the solution is aquo-organic and even more preferably aqueous-alcoholic.
• the pH of this solution can be modified by the possible addition of an acid.
• the compounds which can be introduced into the solution as sources of group VIII elements advantageously are: citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, sulphates, aluminates, molybdates, tungstates, oxides, nitrates, halides for example, chlorides, fluorides, bromides, acetates, or any mixture of the compounds set forth herein.
• molybdenum and tungsten oxides, hydroxides, molybdic and tungstic acids and their salts, in particular sodium salts.
• the oxides or ammonium salts such as ammonium molybdate, ammonium heptamolybdate or ammonium tungstate.
• the preferred phosphorus source is orthophosphoric acid, but its salts and esters such as alkaline phosphates, ammonium phosphate, gallium phosphate or alkyl phosphates are also suitable.
• Phosphorous acids for example hypophosphorous acid, phosphomolybdic acid and its salts, phosphotungstic acid and its salts can be advantageously used.
• a chelating agent of organic nature may advantageously be introduced into the solution if the person skilled in the art deems it necessary.
• all of the metal phase is introduced at the end of the preparation of the support and no additional step is therefore necessary.
• it is chosen to impregnate at least one Group VIB metal, optionally at least one Group VIII metal and optionally the phosphorus element on the previously obtained aluminum oxide support, according to any of the methods of impregnation previously described.
• the product is then generally cured, dried and optionally calcined under an oxidizing atmosphere, for example in air, usually at a temperature of about 300 to 600 ° C, preferably 350 to 550 ° C.
• an oxidizing atmosphere for example in air, usually at a temperature of about 300 to 600 ° C, preferably 350 to 550 ° C.
• the catalyst according to the invention described above undergoes a heat treatment or hydrothermal step.
• this treatment is generally carried out in two stages. At first, the solid is dried at a temperature below 200 ° C. in air, preferably below 150 ° C. In a second step, calcination is carried out in air, without additional addition of water, at a temperature preferably between 300 and 600 ° C, and very preferably between 400 and 500 ° C. In another embodiment, the catalyst does not undergo a complementary heat treatment or hydrothermal step, and the catalyst is only advantageously dried. In this case, the drying temperature is below 200 ° C.
• the catalyst according to the present invention is advantageously used in totally or partially sulphurized form.
• sulpho-reducing atmosphere it therefore undergoes before use an activation step in a sulpho-reducing atmosphere according to any method known to those skilled in the art, in situ or ex situ.
• the sulphurization treatment may be carried out ex situ (before the introduction of the catalyst into the hydrotreatment / hydroconversion reactor) or in situ by means of an organosulfur precursor agent for H 2 S, for example DMDS (dimethyl disulphide),
• the invention describes the use of a catalyst comprising at least one group VI B metal, optionally at least one Group VIII metal, optionally phosphorus, and an aluminum oxide support, in a heavy-lift hydrotreatment process.
• a catalyst comprising at least one group VI B metal, optionally at least one Group VIII metal, optionally phosphorus, and an aluminum oxide support, in a heavy-lift hydrotreatment process.
• a heavy-lift hydrotreatment process such as petroleum residues (atmospheric or vacuum).
• the processes according to the invention advantageously implement the catalyst described according to the invention in hydrotreatment processes for converting heavy hydrocarbon feeds containing sulfur impurities and metal impurities.
• the hydrotreatment processes for converting heavy hydrocarbon feeds, containing sulfur impurities and metal impurities operate at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity advantageously between 0.05 and 10 volumes of filler per volume of catalyst and per hour, and with a hydrogen gas ratio on a hydrocarbon liquid feed advantageously between 100 and 5000 normal cubic meters per cubic meter .
• One objective sought by the use of the catalysts of the present invention relates to an improvement in performance, particularly in hydrodemetallation with respect to catalysts known from the prior art.
• the catalyst described allows improvement in hydrodemetallation (HDM) and hydrodesulphalogenization compared to conventional catalysts, while having a high stability over time. loads
• the feedstocks treated in the process according to the invention are advantageously chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, from a hydroconversion in a fixed bed, in a bubbling bed, or in a moving bed, taken alone or as a mixture.
• These fillers can advantageously be used as they are or else diluted by a hydrocarbon fraction or a mixture of hydrocarbon fractions which may be chosen from the products of the FCC process, a light cutting oil (LCO according to the initials of the English name of Light Cycle Oil), a heavy cutting oil (HCO according to the initials of the English name of Heavy Cycle Oil), a decanted oil (OD according to the initials of the English name of Decanted Oil), a slurry, or From the distillation, gas oil fractions including those obtained by vacuum distillation called according to the English terminology VGO (Vacuum Gas Oil).
• the heavy charges can thus advantageously comprise cuts resulting from the process of liquefying coal, aromatic extracts, or any other hydrocarbon cut.
• Said heavy charges generally have more than 1% by weight of molecules having a boiling point greater than 500 ° C., a cumulative metal content (for example Ni + V) greater than 1 ppm by weight, preferably greater than 20 ppm by weight , very preferably greater than 50 ppm by weight, a content of asphaltenes, precipitated in heptane, greater than 0.05% by weight, preferably greater than 1% by weight, very preferably greater than 2%.
• the heavy fillers can advantageously also be mixed with coal in the form of powder, this mixture being generally called slurry. These fillers can advantageously be by-products from the conversion of the coal and mixed again with fresh coal.
• the coal content in the heavy load is generally and preferably a 1 ⁇ 4 (Oil / Coal) ratio and may advantageously vary widely between 0.1 and 1.
• the coal may contain lignite, be a sub-bituminous coal (according to the English terminology), or bituminous. Any other type of coal is suitable for the use of the invention, both in fixed bed reactors and in bubbling bed reactors.
• the catalyst according to the latter is preferably used in the first catalytic beds of a process comprising successively at least one hydrodemetallization step and at least one hydrodesulfurization step.
• the process according to the invention is advantageously carried out in one to ten successive reactors, wherein the catalyst (s) according to the invention can advantageously be loaded into one or more reactors and / or in all or some of the reactors.
• reactive reactors ie reactors operating alternately, in which hydrodemetallation catalysts (HDM) according to the invention can preferably be implemented, can be used upstream of unit.
• the reactive reactors are then followed by series reactors, in which hydrodesulfurization catalysts (HDS) are used which can be prepared according to any method known to those skilled in the art.
• HDM hydrodemetallation catalysts
• two permutable reactors are used upstream of the unit, advantageously for HDM and containing one or more catalysts according to the invention. They are advantageously monitored by one to four reactors in series, advantageously used for HDS.
• the process according to the invention can advantageously be implemented in a fixed bed with the objective of eliminating metals and sulfur and lowering the average boiling point of the hydrocarbons.
• the operating temperature is advantageously between 320 ° C. and 450 ° C., preferably 350 ° C. to 410 ° C., under a partial pressure.
• in hydrogen advantageously between 3 MPa and 30 MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.05 and 5 volume of charge per volume of catalyst per hour, and with a gaseous hydrogen gas on charge ratio hydrocarbon liquid advantageously between 200 and 5000 normal cubic meters per cubic meter, preferably 500 to 1500 normal cubic meters per cubic meter.
• the process according to the invention can also advantageously be implemented partly in bubbling bed on the same charges.
• the catalyst is advantageously used at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure of advantageously between 3 MPa and 30.degree. MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.1 and 10 volumes of filler per volume of catalyst and per hour, preferably between 0.5 and 2 volumes of filler by volume of catalyst and by hour, and with a gaseous hydrogen gas on hydrocarbon liquid charge advantageously between 100 and 3000 normal cubic meters per cubic meter, preferably between 200 to 1200 normal cubic meters per cubic meter.
• the method according to the invention is implemented in a fixed bed.
• the catalysts of the present invention are preferably subjected to a sulphurization treatment making it possible, at least in part, to convert the metal species into sulphide before they come into contact with the charge. treat.
• This activation treatment by sulphurisation is well known to those skilled in the art and can be performed by any previously known method already described in the literature.
• a conventional sulphurization method well known to those skilled in the art consists in heating the mixture of solids under a stream of a mixture of hydrogen and hydrogen sulphide or under a stream of a mixture of hydrogen and of hydrocarbons containing sulfur-containing molecules at a temperature of temperature between 150 and 800 ° C, preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
• the sulfurization treatment can be carried out ex situ (before the introduction of the catalyst into the hydrotreatment / hydroconversion reactor) or in situ by means of an organosulfur precursor agent of H 2 S, for example DMDS (dimethyldisulphide),
• catalyst supports A and CA For the preparation of catalyst supports A and CA, 5 l of solution are prepared at a concentration of 15 g / l of final alumina and with a contribution rate of the first stage to 2.1 wt. final alumina.
• the co-precipitation pH is maintained between 7 and 10 by controlling the flow rate of the sodium aluminate pump as a priority.
• the suspension is filtered and washed several times.
• the cake is over-dried in an oven for at least one night at 200 ° C.
• the powder is obtained which must be shaped.
• the main characteristics of the gel obtained and engaged in shaping are recalled in Table 1.
• the shaping is carried out on a Brabender kneader with an acid level (total, expressed relative to dry alumina) of 1%, a neutralization rate of 20% and acid and basic fire losses respectively of 62 and 64%.
• the extrusion is carried out on a piston extruder (extrusion speed 50 cm / min and trilobal die diameter 2.1 mm).
• VVH 1 l / h / g with 30% v / v of water, which leads to the extruded CA support.
• the porous distribution of the obtained alumina is characterized by mercury porosimeter intrusion according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle 140 degrees. The absence of microporosity is verified by nitrogen porosimetry.
• the catalyst support AA For the preparation of the catalyst support AA, 5 l of solution are prepared at a concentration of 27 g / l of final alumina and with a contribution rate of the first step to 2.1% by weight of the alumina. final.
• concentrations of the aluminum precursors used are as follows: AI 2 (SO 4 ) 102 g / l Al 2 O 3 and NaAlOO 155 g / l Al 2 O 3 .
• the agitation is 350 rpm throughout the synthesis.
• the co-precipitation pH is maintained between 7 and 10 by controlling the flow rate of the sodium aluminate pump as a priority.
• the suspension is filtered and washed several times.
• the cake is over-dried in an oven for at least one night at 200 ° C.
• the powder is obtained which must be shaped.
• Table 2 Typical characteristic of the gel used for the preparation of alumina.
• the shaping is carried out on a Brabender kneader with an acid level (total, expressed relative to dry alumina) of 1%, a neutralization rate of 20% and acid and basic fire losses respectively of 62 and 64%.
• the extrusion is carried out on a piston extruder (extrusion rate 50 cm / min and trilobal die diameter 2.1 mm).
• the porous distribution of the obtained alumina is characterized by mercury porosimeter intrusion according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle 140 degrees. The absence of microporosity is verified by nitrogen porosimetry.
• the first step is a rapid dehydration of 20.61 g gibbsite at high temperature (800 ° C) and low contact time (0.8 sec), allowing a transition alumina powder to be obtained ⁇ (chi).
• a washing allowing the reduction of the Na 2 0 content was carried out using water (3 kg / kg Al 2 O 3 ), followed by a second rapid dehydration treatment similar to the previous one, also allowing to obtain an alumina powder. This powder is shaped by granulation in a bezel.
• catalyst supports D and CD For the preparation of catalyst supports D and CD, 5 l of solution are prepared at a concentration of 40 g / l of final alumina (non-compliant) and with a contribution rate of the first stage to 2.1. % by weight of the total alumina.
• the co-precipitation pH is maintained between 7 and 10 by controlling the flow rate of the sodium aluminate pump as a priority.
• the suspension is filtered and washed several times.
• the cake is over-dried in an oven for at least one night at 200 ° C.
• the powder is obtained which must be shaped.
• the shaping is carried out on a Brabender kneader with an acid level (total, expressed relative to dry alumina) of 1%, a neutralization rate of 20% and acid and basic fire losses respectively of 62 and 64%.
• the extrusion is carried out on a piston extruder (extrusion speed 50 cm / min and trilobal die diameter 2.1 mm).
• the extrudates obtained are dried at 100 ° C. overnight and then calcined.
• VVH 1 l / h / g with 30% v / v of water, which leads to the extruded support CD.
• the porous distribution of the obtained alumina is characterized by mercury porosimeter intrusion according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle 140 degrees. The absence microporosity is verified by nitrogen porosimetry.
• the synthesis of a non-compliant alumina gel is first carried out in that it is synthesized according to the preparation method described in US Pat. No. 7,790,562.
• the synthesis is carried out in a reactor of 7 I and a final suspension of 5 I in 2 precipitation stages.
• the amount of water added to the reactor is 3960 ml.
• the final concentration of alumina is 30g / l.
• the agitation is 350 rpm throughout the synthesis.
• the temperature of the reaction medium is maintained at 30 ° C.
• a suspension containing a precipitate of alumina is obtained.
• the flow rate of the aluminum sulphate precursors Al 2 (SO 4 ) and aluminum aluminate NaAlO 4 introduced in the first precipitation step are respectively 19.6 ml. / min and 23.3 ml / min.
• a suspension containing a precipitate of alumina is obtained.
• the flow rate of the aluminum sulphate precursors Al 2 (SO 4 ) and sodium aluminate NaAlOO containing aluminum introduced in the second precipitation stage are respectively 12.8 ml. / min and 14.1 ml / min.
• Shaping of the alumina gel The shaping is carried out on a Brabender type kneader with an acid level (total, expressed relative to dry alumina) of 3%, a neutralization rate of 40% and acid and basic fire losses of 61% and 63% respectively.
• the extrusion is carried out on a piston extruder (extrusion speed 50 cm / min and trilobal die diameter 2.1 mm).
• the porous distribution of the obtained alumina is characterized by mercury porosimeter intrusion according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle 140 degrees. The absence of microporosity is verified by nitrogen porosimetry.
• Catalysts A1, AA1, CA1, B1, D1, CD1, E1, CE1 were respectively prepared from supports A, AA, CA, B, D, CD, E, and CE. To do this, the method of dry impregnation was used.
• the aqueous solution of the impregnation contains salts of molybdenum, nickel as well as phosphoric acid (H 3 PO 4 ) and hydrogen peroxide (H 2 O 2 ).
• the molybdenum salt is ammonium heptamolybdate ⁇ 7 ⁇ 24 ( ⁇ 4) 6 .4 ⁇ 2 0 and that of nickel is nickel nitrate Ni (N0 3 ) 2 -6H 2 0.
• the amounts of each of these salts in solution have were determined so as to deposit the desired amount of each element in the catalyst.
• the extrudates of the impregnated support are dried overnight at 120 ° C. and then calcined at 500 ° C. for 2 hours in air.
• the target content of molybdenum trioxide is 6% by weight, that of nickel oxide is 1.5% by weight, and that of phosphorus pentoxide is 1.2% by weight.
• the atomic ratio P / Mo is equal to 0.4 and the atomic ratio Ni / Mo is equal to 0.49.
• Example 6 HDT Evaluation of Residues of Catalysts A1, AA1, CA1 (According to the Invention) Compared with Catalysts B1, D1, CD1, E1, and CE1 (Comparative)
• the catalysts A1, CA1 and AA1 prepared according to the invention, but also the comparative catalysts B1, D1, CD1, E1, and CE1 were subjected to a catalytic test in a perfectly stirred batch reactor, on a vacuum residue type load RSV Safanyia (Heavy Arabian, see characteristics in Table 4).
• the reactor is cooled and after a triple stripping of the atmosphere under nitrogen (10 minutes at 1 MPa), the effluent is collected and analyzed by fluorescence X-rays (sulfur and metals) and by simulated distillation (ASTM D7169).
• the hydrodesulfurization rate HDS is defined as follows:
• HDS (%) ((% wt S) c arge - (wt% S) Rec etie) / (wt% S) cha rge X 100
• HDM hydrodemetallization rate ((ppm wt Ni + V) load - (ppm wt Ni + V) recipe ) / (ppm wt Ni + V) load x 100
• HDX 4o + 5 (%) ((X540 +) charge-(X540 +) effluent) / (X540 +) load 100
• CA1 (according to the invention) 48.6 79.1
• CE1 (comparative) 52.8 70.4 It is deduced from Table 6 that the implementation of the catalysts of the present invention generates a significant gain in hydrodemetallation (HDM) which is never observed for the different textures of the existing art. A slight degradation in hydrodesulphurization (HDS) is observed, but is not unacceptable for the purpose of performing tests in sequence, as is the case industrially.
• HDM hydrodemetallation
• the origin of the differences in activity is explained by the fact that the carriers conforming to A, AA, CA1 simultaneously have a mesoporous volume above 0.75 ml / g, a porous diameter at least equal to 18 nm, a macroporous volume of at least 15% of the total volume and a S B ET greater than 100 m 2 / g.
• the supports CD and CE have porous diameters that are too low
• the supports D, E, CD and CE have macroporous volumes that are too low
• the support B has a mesoporous volume that is too low.
• the described catalysts A1, AA1, CA1 prepared according to the invention were compared in a petroleum residue hydrotreatment test with, in comparison, the performances of the catalysts B1, D1 and E1.
• the charge consists of a mixture of an atmospheric residue (RA) of Middle Eastern origin (Arabian medium) and a vacuum residue (Arabian Light). Two separate mixtures were made for these evaluations.
• the corresponding charges are characterized respectively by high contents of Conradson carbon (13.2 and 14.4% by weight) and asphaltenes (5.2 and 6.1% by weight) and a high amount of nickel (22 to 25 ppm by weight), vanadium (67 to 79 ppm by weight) and sulfur (3.86 to 3.90% by weight).
• Table 7 Characteristics of the loads n ° 1 and n ° 2 used for the tests
• the support F was prepared following the method of preparation of Example 3 of US Pat. No. 6,780,817.
• the porous distribution of the alumina obtained is characterized by mercury porosimeter intrusion according to the ASTM D4284-83 standard. a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °. The absence of microporosity is verified by nitrogen porosimetry.
• Table 3 Catalyst F1 was prepared from support F previously obtained. To do this, the method of dry impregnation was used.
• the aqueous solution of the impregnation contains salts of molybdenum, nickel as well as phosphoric acid (H 3 PO 4 ) and hydrogen peroxide (H 2 O 2 ).
• the molybdenum salt is ammonium heptamolybdate ⁇ 7 ⁇ 24 ( ⁇ 4) 6.4 ⁇ 2 0 and that of nickel is nickel nitrate ⁇ ( ⁇ 0 3) 2 -6 ⁇ 2 0.
• the amounts of each of these salts in solution were determined so as to deposit the desired amount of each element in the catalyst.
• the extrudates of the impregnated support are dried overnight at 120 ° C. and then calcined at 500 ° C. for 2 hours in air.
• the target content of molybdenum trioxide is 6% by weight, that of nickel oxide is 1.5% by weight, and that of phosphorus pentoxide is 1.2% by weight.
• the atomic ratio P / Mo is equal to 0.4 and the atomic ratio Ni / Mo is equal to 0.49.
• the concentrations in solutions have therefore been adjusted to meet this target, taking into account the volume of water uptake of the various supports, the latter being determined classically, as is well known to those skilled in the art.
• the molybdenum salt is ammonium heptamolybdate ⁇ 7 ⁇ 24 ( ⁇ 4) 6 .4 ⁇ 2 0 and that of nickel is nickel nitrate Ni (N0 3 ) 2 .6H 2 0.
• the amounts of each of these salts in solution have determined so as to deposit the desired amount of each element in the catalyst.
• the extrudates of the impregnated support are dried overnight at 120 ° C. and then calcined at 500 ° C. for 2 hours in air.
• the target molybdenum trioxide content is 8% by weight, that of nickel oxide is 1.5% by weight, and that of the phosphorus pentoxide is 2.3% by weight.
• the atomic ratio P / Mo is equal to 0.58 and the atomic ratio Ni / Mo is equal to 0.37.
• the concentrations in solutions have therefore been adjusted to meet this target, taking into account the volume of water uptake of the various supports, the latter being determined classically, as is well known to those skilled in the art.
• the target content of molybdenum trioxide is 4.5% by weight, that of nickel oxide is 1.1% by weight, and that of phosphorus pentoxide is 1.5% by weight.
• the atomic ratio P / Mo is equal to 0.67 and the atomic ratio Ni / Mo is equal to 0.49.
• concentrations in solutions were therefore adjusted to meet this target, taking into account the volume of water uptake of the various supports, the latter being determined classically, as is well known to those skilled in the art.
• the performances obtained on the catalysts A2, AA2, and A3, AA3 indicate that the combination of the textural properties of the supports A and AA with different catalytic formulations as claimed in the present application systematically makes it possible to maximize the performance in hydrodemetallation HDM compared to the same formulation deposited on a support with different textural properties, and in particular described in the prior art.
• the level of performance in hydrodemetallation HDM achieved is in particular systematically higher than that achievable using the supports and formulations of the prior art.
• Example 11 Stability assessment over a period of 3000 hours (approximately 4 months)
• the catalyst according to the invention A1, as well as the comparative catalyst E1, were evaluated in hydrodemetallization for 3,000 hours on the feed No. 2 of Table 5 while maintaining a target of 30 ppm of metals (Ni and V cumulated) in the effluent. To do this the temperature has been gradually increased over time to compensate for the deactivation.
• the sulfur content at the unit outlet is higher than that observed with the reference catalyst E1.
• the deactivation is low (1, 6 ° C / month, Figure 6), which allows to maintain a low operating temperature and in accordance with the constraints of the refiner.
• the mechanical properties of the catalysts A1, and E1 were evaluated by a mechanical strength test (EGG) according to ASTM D6175. Their average mechanical strength is 0.9 daN / mm for the catalyst A1, which is satisfactory for the considered applications and higher than what can be observed for other catalysts of the prior art, such as E1 which has an EGG equal to 0.8 daN / mm.

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